Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
  • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone

Definitions

• organic polymers such as those obtained by polymerization (or copolymerization) of mono- and diolefins which may contain functional groups, or by polycondensation of suitable precursors, for example diols with dicarboxylic acids, under the action of air / oxygen Heat, light or high-energy radiation can undergo changes that affect the important properties of the polymers, such as strength, hardness and elongation. Such damage often results not only in a significant change in the measurable physical properties, but also in a visually noticeable softening, embrittlement and / or discoloration of the finished parts. For this reason, stabilizers are added to the corresponding polymers before processing. For further details, we refer to the summary work by G.
• Esters of 3,5-dialkyl-4-hydroxyphenyl (alkane) carboxylic acids are described, for example, in US Pat. Nos. 4,598,113, 3,681,431, 3,330,859, 3,644,482, 3,285,855, esters of 4,6- Dialkyl-3-hydroxyphenyl (alkane) carboxylic acids in U.S. PSS 3 988 363, 3 862 130 and esters of 2-methyl-4-tert-butyl-5-hydroxyphenyl- (alkane) -carboxylic acids in EP-PS 0 048 841.
• the effect of the phenolic stabilizers can often be increased by adding certain, mostly sulfur or phosphorus-containing compounds.
• the optimum quantitative ratio of stabilizer and synergist must always be determined experimentally in individual cases. It applies to both the stabilizers and to the synergists that they should be incorporated into the various polymers without decomposition without difficulty and should be distributed as evenly as possible therein.
• the polymer should neither discolor due to the additives nor suffer a reduction in molecular weight due to the temperature and shear stress.
• the object of the invention was, based on known 3-tert-butyl or. 3-tert-butyl-5-alkyl-4-hydroxyphenyl- (alkane) -carboxylic acids or their derivatives, preferably of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid (derivatives), by reaction with selected, alcohols which are economical to prepare and contain at least two hydroxyl groups and optionally sulfur as heteroatom to give esters of these 3-tert-butyl or.
• 3-tert-butyl-5-alkyl-4-hydroxyphenyl- (alkane) -carboxylic acids of the formula I preferably those of 3,5-di-tert-butyl-4-hydroxyphenyl-propionic acid, are converted and if these, the esters containing poly (monooxethylates) as the alcohol component are used to stabilize the abovementioned polymers.
• esters according to the invention based on oxethylates of bis- (4- or 2-hydroxyphenyl) alkanes and heteroatom-containing analogues or of tris (4-hydroxyphenyl) alkanes or 1,3 , 5-tris- (4-hydroxyphenyl-isopropylidene) -arylene stabilizers to be mixed in at the high temperatures of polyolefin processing can be obtained with good effectiveness and surprisingly little discoloration of the polymer materials provided with them. This is all the more surprising since, according to the prior art, for example according to US Pat. No.
• esters of (di-alkyl-4-hydroxyphenyl) alkane-carboxylic acids with alpha, omega-bis containing ether groups - Hydroxyethyl- (poly) -oxaalkanes of the formula IV HO (CH 2 ) " (O (CH 2 ) m ) P O (CH 2 ) 1 OH (IV) with m, n, I 2, p ⁇ 0 lead to discoloration in polyolefins, so that such products are not recommended for this important area of application.
• the stabilizers according to the invention show no loss of effectiveness even if the bis- (phenols) and tris (phenols) of the formulas II and III to be ethoxylated have the ortho-standing position for the phenolic hydroxyl group required for their stabilizing action Do not have alkyl groups, which considerably facilitates the oxethylation.
• Bis- (4- or 2-hydroxyphenyl) alkanes or Cycloalkanes of the formula II and tris (4-hydroxyphenyl) compounds of the formula III should be preferred in the context of the invention as starting materials for the polyols to be esterified.
• esters to be used according to the invention preferably in polypropylene and polyethylene as stabilizers are new compounds, the characterization of which by melting points and spectroscopic studies can be found in the attached examples. Such crystalline compounds are preferred over liquid stabilizers because their uniform distribution in polymers such as polyethylene or polypropylene and the continuous addition of the necessary small amounts to polymer powders i. a. cause less difficulty.
• the preparation of the esters according to the invention can be carried out by processes known per se by reacting reactive acids of the formula I or of their derivatives with the bi- or. polyfunctional alcohols. These should contain at least two or three alkylene oxide units, preferably ethylene oxide units, the ether bridges formed in the oxethylation starting from two or three different hydroxyl groups.
• Very particularly preferred precursors are di- (or poly -) (monooxethylates) of bis- (4- or 2-hydroxyphenyl) alkanes, oxides, sulfides and sulfones or tris (4-hydroxyphenyl) - alkanes and aryls in which all phenolic hydroxyl groups have been converted into 2-hydroxyethyl groups by the action of ethylene oxide.
• Such bis (or poly) (2-hydroxyethoxyaryl) alkanes, oxides, sulfides, sulfones and aryls have not been previously described for all compounds corresponding to formulas II and III.
• the desired diols (or polyols) can be separated off from by-products, such as polyglycols or higher oxethylates, which may have formed during the oxyethylation, by known processes of the prior art, ie, for example, by crystallization from suitable solvents (such as alcohols or ethers) or by Column chromatography.
• Esters with oxyethylates of compounds of the formulas II and III are particularly preferred, each of which contains an ethylene oxide unit (as a 2-hydroxyethoxy group) instead of the hydroxyl groups of the compounds of the formulas II and III, in particular esters with bis or.
• m-diisopropylbenzene ie 1,4-or 1,3-bis- [alpha- (4-hydroxyphenyl] -ispropylidene) benzene or 1,4-or 1,3-di- [1- (4-hydroxyphenyl- ) -1-methyl-ethyl] -phenylene
• 1,1-bis- (4-hydroxy-3-tert-butylphenyl) -cycododecane 1,1-bis- (4-hydroxyphenyl) -1-phenyl-ethane, 2,2-bis- (4-hydroxy-3-tert-butylphenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydrophenyl) ethane and 1,3,5-tris (4-hydroxyphenyl isopropylidene) benzene.
• esters according to the invention are particularly simple if the bis (or poly) (monooxethylates) which can be prepared from compounds of the formulas II or III with esters of 3-tert-butyl or. 3-tert-butyl-5-alkyl-4-hydroxyphenyl- (alkane) -carboxylic acids of the formula I, preferably with esters of 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionic acid, the Contain alkoxy groups with one to four carbon atoms, are transesterified with the release and removal of the more volatile alcohols. The transesterification is generally carried out at elevated temperature, preferably below 125 ° C.
• the transesterification is expediently carried out under inert gas or under reduced pressure in order to prevent oxidation of feed or. Avoid reaction products and to keep the thermal load on the reaction mixture low, especially in the presence of the transesterification catalysts. It is advantageous to use one of the starting materials in a 10 to 20% molar excess beyond the stoichiometric amount required.
• the reaction is interrupted as soon as extensive (or complete) consumption of the component used in the deficit has been demonstrated by analysis of the reaction mixture or by weighing the separated alcohol.
• the catalyst is inactivated (ie destroyed in the case of basic or neutral catalysts, for example by adding an equivalent amount of acid), the reaction mixture is worked up and the diol (or polyol) esters are recrystallized from suitable solvents, such as. As alcohols, ethers or aromatic hydrocarbons, cleaned. Subsequently, the constitution of the compounds I will H-NMR spectroscopy secured based on the position and intensity of the various signals.
• Poly- [4 or. 2- (2'-hydroxyethoxy) aryl] alkanes, oxides, sulfides and sulfones or aryls are valuable stabilizers for polymers, preferably for (co) polymers of mono- and / or diolefins, in particular polypropylene and polyethylene. They can be used as processing stabilizers, but also as long-term stabilizers. Mixing into the polymers can be carried out by known methods of the prior art by mixing the powdery polymers with the stabilizers or with a stabilizer concentrate (in the respective polymer).
• the stabilizer additive can also be introduced into a suspension, emulsion or solution of the polymers before the workup will.
• the stabilizers are generally used in amounts of 0.02 to 3 percent by weight of the material to be stabilized, but the optimum amount which can be easily determined by the person skilled in the art varies depending on the polymer to be stabilized and the type of stress.
• An advantageous range is between 0.05 and 2 percent by weight of stabilizer additive; additions of 0.1 and 1 percent by weight are particularly favorable for polyolefins. Individual esters, but also mixtures of several, can optionally be added.
• various other additives such as.
• organic sulfur and / or phosphorus-containing compounds as synergists, but also stabilizers, plasticizers, pigments, UV stabilizers, antistatic agents, fillers and / or processing aids, such as calcium stearate, not according to the invention, are additionally incorporated into the polymers.
• the stabilization according to the invention of polymers which, in the case of the polyolefins, can be processed to give versatile finished parts by the injection molding or extrusion process is illustrated by the following examples.
• the constitution of the bis-ester is confirmed by the position and intensity of the absorption lines of the 1 H-NMR spectrum (see Table I).
• the constitution of the bis-ester is confirmed by the position and intensity of the absorption lines of the 1 H-NMR spectrum (see Table I).
• the constitution of the bis-ester is confirmed by the position and intensity of the absorption lines of the 1 H-NMR spectrum (see Table I).
• 2 kg of polypropylene powder are mixed with the amounts of stabilizer specified in Table III (esters according to the invention in Examples 22 to 27 or stabilizers according to the prior art in Examples 28 to 32), calcium stearate as processing aid and bis (octadecyl ) -thiodipropionic acid ester and optionally on tris (2,4-di-tert-butylphenyl) phosphite and in a mixing unit (e.g. fluid mixer from Papenmeier) at room temperature for a short time (approx. 1 Minute) mixed.
• the powder mixtures obtained are extruded at 100 rpm and a maximum of 230 ° C.
• polypropylene granules provided according to Examples 22 to 27 with stabilizers according to the invention and optionally further additives are pressed at 210 ° C. into sheets (dimensions 4 ⁇ 10 ⁇ 100 mm). After 4 weeks of storage at 100 ° C., these are assessed with regard to possible color changes compared to samples that are not thermally stressed and in comparison with samples aged analogously at 100 ° C. with stabilizers not according to the invention (Examples 37 to 39).
• Table IV contains visually determined color impressions, which are based on analog aged comparison samples with the tetra or.
• the suitability of the stabilizers used as processing stabilizers is checked on the basis of the 15 values determined at 190.degree. C., by means of which the extent of a molecular weight degradation which is occurring can be recognized.
• Table V contains the measured values which show the effects of multiple extrusion in the presence of the stabilizers according to the invention (according to Examples 12, 13, 17 and 19) or two stabilizers according to the prior art (bis or tetra- [3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionic acid] ester of 2,2-bis [4' - (2 "-hydroxyethoxy) phenyl] propane (Example 44) and des Play pentaerythrits (example 45).
• polypropylene powder is mixed with 0.1% by weight of the various stabilizers according to the invention, which were produced according to Examples 14, 16, 20 and 21, or with a stabilizer according to the prior art ( Tetra- [3- (3,5-di-tert-butyl-4-hydroxyphenyl-) propionic acid -] - ester of pentaerythritol) and with 0.1% by weight calcium stearate as processing aid and optionally additionally with 0.1% by weight bis- (octadecyl -) - Thiodipropionic acid ester (Abb.
• test results show that the discoloration stabilized according to the invention (Examples 72 to 75) does not in any case cause more discolouration than the material stabilized according to the prior art (Example 76 not according to the invention), the degree of discoloration being low in all test specimens.
• the Is values (MFI) measured on the granules obtained at 190 ° C. are shown in Table VIII.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 1986
  • 1986-11-18 DE DE19863639374 patent/DE3639374A1/de not_active Withdrawn
• 1987
  • 1987-09-21 EP EP87113763A patent/EP0271649B1/fr not_active Expired - Lifetime
  • 1987-09-21 DE DE8787113763T patent/DE3773865D1/de not_active Expired - Lifetime
  • 1987-11-17 JP JP62290461A patent/JPS63135358A/ja active Pending
  • 1987-11-18 US US07/123,425 patent/US4912249A/en not_active Expired - Fee Related

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